CN109265470A - A kind of linear organic hole transport material and its preparation and application - Google Patents
A kind of linear organic hole transport material and its preparation and application Download PDFInfo
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Abstract
The present invention discloses a kind of linear organic hole transport material and its preparation and application, linear organic hole transport material of the invention is using the coplanar thiophene condensed hetero ring of rigidity as parent core, the molecular configuration of its linear plane can effectively promote hole mobility and conductivity, which has good dissolution filming performance and excellent photo and thermal stability.The preparation method synthetic route of the linear organic hole transport material of the present invention is simple, raw material is easy to get, is low in cost, and when being applied in perovskite solar battery, battery device circuit photocurrent density reaches 22.31mA cm‑2, open-circuit voltage 1.094V, fill factor 0.756, incident photon-to-electron conversion efficiency reaches 18.45%, improves the efficiency of perovskite solar battery, has broad application prospects.
Description
Technical field
The invention belongs to technical field of solar batteries, specifically a kind of linear organic hole transport material and its preparation and
Using.
Background technique
As photovoltaic science and technology of new generation, perovskite solar battery (Perovskite Solar Cells, abbreviation PSCs)
Have many advantages, such as that the easy modulation of material, high-efficient, preparation process is simple, low in cost.The hole transmission layer group important as PSCs
At part, main function is to collect and transmit by perovskite absorbed layer injected holes, realizes that electron-hole efficiently separates, this
Process plays important influence to battery efficiency.Hole mobile material is broadly divided into organic hole transport material and inorganic hole passes
Defeated material two major classes.The selectable range of inorganic hole transporter is relatively narrow, and the photoelectric conversion efficiency of respective devices is relatively low；
And organic hole transport material, since MOLECULE DESIGN is flexible, spectrum and energy level can easily be accommodated, and therefore, research and develop novel organic hole
Transmission material is to improve the effective means of battery efficiency and stability.
Patent CN105037179B discloses a kind of novel hole transport material and its preparation method and application, can reach
To 11.3% incident photon-to-electron conversion efficiency；Patent CN106748832B discloses the hole based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shell
Transmission material can reach 12.95% incident photon-to-electron conversion efficiency；Patent CN107915744A discloses one kind with dithieno
Pyrroles reaches 16.2% for the organic hole transport material of core and its preparation and application, incident photon-to-electron conversion efficiency.Although at present in sky
Made some progress in the research of hole transport materials, but cost, stability and in terms of still
In the presence of very big room for improvement.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of linear organic hole transport materials.
Another object of the present invention is to provide the preparation methods of above-mentioned linear organic hole transport material.
It is also an object of the present invention to provide the applications of above-mentioned linear organic hole transport material, can be used for preparing
Perovskite solar battery.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of linear organic hole transport material, the chemical structural formula with following formula (VII):
Linear organic hole transport material of the invention is using the coplanar thiophene condensed hetero ring of rigidity as parent core, linearly
The molecular configuration of planarization can effectively promote hole mobility and conductivity, which has good dissolution filming performance and excellent
Different photo and thermal stability.
The present invention also provides the preparation methods of above-mentioned linear organic hole transport material, comprising the following steps:
Step 1, prepare compound I, compound III and compound VI, the structural formula of the chemical compounds I are as follows:
The structural formula of the compound III are as follows:
The structural formula of the compound VI are as follows:
Chemical compounds I is first reacted with lithium diisopropylamine, then reacts with anhydrous cupric chloride and generate compound by step 2
II, the structural formula of the compound ii are as follows:
Compound ii and compound III are carried out Buchwald-Hartwig and are coupled cyclization reaction, generate chemical combination by step 3
Object IV, the structural formula of the compounds Ⅳ are as follows:
Compounds Ⅳ is first acted on n-BuLi, then reacts with tributyltin chloride and generate compound V, institute by step 4
State the structural formula of compound V are as follows:
Compound V and compound VI are carried out Still coupling reaction, generate compound VII, the compound by step 5
VII i.e. linear organic hole transport material.
The reaction equation of preparation method of the present invention is as follows:
A kind of preparation method synthetic route of linear organic hole transport material of the invention is simple, raw material is easy to get, cost
It is cheap.
Further, the step 2 are as follows: under argon gas protection and condition of ice bath, make chemical compounds I and diisopropylaminoethyl
Lithium reacts 1~3h, then anhydrous cupric chloride is added into reaction system, the reaction was continued under condition of ice bath 1~3h, be warming up to room temperature after
8~16h of continuous reaction, through isolating and purifying to obtain compound ii；The chemical compounds I, lithium diisopropylamine and anhydrous cupric chloride
The ratio of the amount of substance is 1:0.8~1.2:0.8~1.2.
Further, the step 3 are as follows: under argon gas protective condition, in dry toluene solvent, make compound ii and change
It closes object III to be heated to reflux under the catalytic action of palladium catalyst, organophosphor ligand and organic base, Buchwald-Hartwig occurs
Coupling reaction, the reaction time is 4~12h, through isolating and purifying to obtain compounds Ⅳ；It is the compound ii, compound III, organic
The ratio of the amount of the substance of alkali, palladium catalyst and organophosphor ligand is 1:1~1.5:2~8:0.02~0.1:0.04~0.2.
Further, the step 4 are as follows: under argon gas protective condition, in anhydrous tetrahydro furan solvent, make compounds Ⅳ
2h is reacted with n-BuLi under the conditions of -78 DEG C, tributyltin chloride is then added, is warming up to room temperature, the reaction was continued 4~12h,
Obtain compound V；The ratio of the amount of the substance of the compounds Ⅳ, n-BuLi and tributyltin chloride be 1:2~2.5:2~
2.5。
Further, the step 5 are as follows: under argon gas protective condition, in toluene solution, make compound V and compound
VI is heated to reflux generation Stille coupling reaction under the catalysis of tetra-triphenylphosphine palladium, and the reaction time is 4~12h, pure through separating
Change obtains compound VII, and compound VII is linear organic hole transport material；The compound V, the triphenyl of compound VI and four
The ratio of the amount of the substance of phosphine palladium is 1:2~3:0.05~0.1.
Further, in step 3, the palladium catalyst is palladium chloride, tris(dibenzylideneacetone) dipalladium, [1,1'-
Bis- (diphenylphosphino) ferrocene] one of palladium chloride or four triphenyl phosphorus palladiums or a variety of, the organophosphor ligand is three
Bis- (diphenylphosphine) ferrocene of tert-butyl phosphine, 1,1'- or 2,2'- is bis--one of (diphenyl phosphine) -1,1'- dinaphthalene or a variety of,
The organic base is one or both of sodium tert-butoxide or potassium tert-butoxide.
The present invention also provides application of the above-mentioned linear organic hole transport material in perovskite solar battery.
When organic hole transport material of the invention is applied in perovskite solar battery, battery device short-circuit photocurrent
Density reaches 22.31mA cm-2, and open-circuit voltage 1.094V, fill factor 0.756, incident photon-to-electron conversion efficiency reaches 18.45%, mentions
The high efficiency of perovskite solar battery.
Compared with prior art, the beneficial effects of the present invention are:
1, linear organic hole transport material of the invention is using the coplanar thiophene condensed hetero ring of rigidity as parent core, line
Property planarization molecular configuration can effectively promote hole mobility and conductivity.
2, linear organic hole transport material of the invention has good dissolubility energy and excellent photo and thermal stability.
3, the preparation method synthetic route of linear organic hole transport material of the invention is simple, raw material is easy to get, is at low cost
It is honest and clean.
4, when organic hole transport material of the invention is applied in perovskite solar battery, battery device short circuit photoelectricity
Current density reaches 22.31mA cm-2, open-circuit voltage 1.094V, fill factor 0.756, incident photon-to-electron conversion efficiency reaches 18.45%, mentions
The high efficiency of perovskite solar battery.
Detailed description of the invention
Fig. 1 is the thermogravimetric test result of the linear organic hole transport material of the embodiment of the present invention 1；
Fig. 2 is the conductivity test result figure of the linear organic hole transport material of the embodiment of the present invention 1；
Fig. 3 is the hole mobility test result figure of the linear organic hole transport material of the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the linear organic hole transport material of the embodiment of the present invention 1；
Fig. 5 is perovskite solar battery structure schematic diagram prepared by the embodiment of the present invention 1；In figure: 1, metal electrode, 2,
Hole transmission layer, 3, perovskite photosensitive layer, 4, electron transfer layer, 5, electro-conductive glass；
Fig. 6 is the I-V curve figure of perovskite solar battery prepared by the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the embodiment in the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, those of ordinary skill in the art's all other embodiment obtained under the conditions of not making creative work all belongs to
In the scope of protection of the invention.
A kind of linear organic hole transport material, the chemical structural formula with following formula (VII):
The preparation method of above-mentioned linear organic hole transport material, reaction equation are as follows:
Compound used therefor I of the present invention is according to document Han, J.；Zheng,X.；Wang,Y.；Hu,L.Guo,C.；Wang,Y.；
Li,Y.；Ma,D.；Qiao,W.；Wang, Z.J.Mater.Chem.C, 2017,5,159-165 preparation synthesis；Compound III according to
Document Wang, Z.；Liang,M.；Tan,Y.；Ouyang,L.；Sun,Z.；Xue.S.J.Mater.Chem.A 2015,3,
4865-4874 are prepared；Compound VI is according to document Rakstys, K.；Abate,A.；IbrahimDar, M.；Gao, P.；
Jankauskas, V.；Jacopin, G.；Kamarauskas, E.；Kazim, S.；Ahmad, S.；M.；
Nazeeruddi, M.K.J.Am.Chem.Soc.2015,137,16172-16178 are prepared；Other reaction reagents are bought
It obtains.
Embodiment 1
A kind of linear organic hole transport material, the chemical structural formula with following formula (VII):
The preparation method of above-mentioned linear organic hole transport material, reaction equation are as follows:
Above-mentioned linear organic hole transport material, is prepared by following steps:
Step 1, prepare compound I, compound III and compound VI, chemical compounds I is according to document Han, J.；Zheng,X.；
Wang,Y.；Hu,L.Guo,C.；Wang,Y.；Li,Y.；Ma,D.；Qiao,W.；Wang,Z.J.Mater.Chem.C,2017,5,
159-165 preparation synthesis；Compound III is according to document Wang, Z.；Liang,M.；Tan,Y.；Ouyang,L.；Sun,Z.；
Xue.S.J.Mater.Chem.A 2015,3,4865-4874 is prepared；Compound VI is according to document Rakstys, K.；
Abate, A.；IbrahimDar, M.；Gao, P.；Jankauskas, V.；Jacopim, G.；Kamarauskas, E.；Kazim,
S.；Ahmad, S.；M.；Nazeeruddi, M.K.J.Am.Chem.Soc.2015,137,16172-16178 are prepared into
It arrives.
20mL anhydrous tetrahydro furan is added into reaction flask as molten under conditions of argon gas protection and ice bath for step 2
Agent is added 2.19g chemical compounds I and is uniformly mixed, then the lithium diisopropylamine solution of 2mol/L is added dropwise to reaction system
In；It is added dropwise, reaction solution continuation reacts 1h under ice bath；Anhydrous cupric chloride is added in reaction system, the compound
I, the ratio of the amount of the substance of lithium diisopropylamine and anhydrous cupric chloride is 1:1:1, after the 1h that is maintained under ice bath that the reaction was continued, instead
Liquid is answered to be to slowly warm up to the continuous reaction 8h of room temperature；Water quenching on the rocks is gone out, and ethyl acetate extraction, anhydrous magnesium sulfate is dry, and vacuum distillation removes
Remove solvent；Crude product obtains compound ii through column chromatography (eluent: petroleum ether/methylene chloride=15/1) purification, obtained change
Conjunction object II is light yellow solid, and the yield of this step compound of reaction II is 61%.
Step 3 sequentially adds 872mg compound ii, sodium tert-butoxide, three into three-necked flask under the protection of argon gas
Bis- (diphenylphosphine) ferrocene of (dibenzalacetone) two palladium, 1,1'-, compound III and 25mL dry toluene, the compound
II, the amount of the substance of compound III, sodium tert-butoxide, tris(dibenzylideneacetone) dipalladium and bis- (diphenylphosphine) ferrocene of 1,1'-
Ratio be 1:1.3:4:0.05:0.2；Reaction system is heated to 110 DEG C of reaction 8h, is cooled to room temperature, and vacuum distillation removes solvent,
Crude product obtains compounds Ⅳ through column chromatography (eluent: petroleum ether/methylene chloride=15/1) purification, and obtained compounds Ⅳ is
Faint yellow solid, the yield of this step compound of reaction IV are 91%.
468mg compounds Ⅳ and anhydrous is added into round bottom reaction flask in argon gas protection and under the conditions of -78 DEG C for step 4
Tetrahydrofuran, then n-BuLi (2.5mol/L) is added dropwise in reaction system.It is added dropwise, reaction solution continues -78
2h is reacted at DEG C, and tributyltin chloride is added in reaction system, the compounds Ⅳ, n-BuLi and tributyltin chloride
Substance amount ratio be 1:2.4:2.4；Reaction solution is to slowly warm up to room temperature the reaction was continued 8h；Water quenching on the rocks is gone out, ethyl acetate
Extraction, anhydrous magnesium sulfate is dry, and vacuum distillation removes solvent；Crude product need not purify, and be directly used as the next step.
Step 5, under argon gas protective condition, into three neck round bottom flask, successively by compound V, 922mg compound VI,
The ratio of tetrakis triphenylphosphine palladium and 20mL toluene, the amount of the substance of the compound V, compound VI and tetra-triphenylphosphine palladium is
1:2.4:0.1；Reaction system is heated to 80 DEG C of reaction 8h and is cooled to room temperature, and vacuum distillation removes solvent；Crude product is chromatographed through column
(eluent: petroleum ether/methylene chloride=6/1) purification obtains compound VII, and compound VII is linear organic hole transport material,
Compound VII is yellow solid, and VII gross production rate of compound of two step of step 4 and step 5 is 35%.
Linear organic hole transport material manufactured in the present embodiment is tested, test temperature by thermogravimetry (TGA)
Range is 0~800 DEG C, and heating rate is 5 DEG C/min, test result (see Fig. 1) display: the linear organic hole transmission of the present embodiment
The decomposition temperature of material VII is 394 DEG C, shows it with preferable thermal stability.
Linear organic hole transport material manufactured in the present embodiment, by current -voltage curve testing conductivity, as a result such as
Shown in Fig. 2.Conductivityσ=L/Rwd, wherein 1/R is current -voltage curve slope, and L is constant 0.05cm, and W is constant
0.2cm, d are hole transmission layer film thickness；It is 2.82 by the conductivity that linear organic hole transport material VII is calculated in formula
×10-3S.cm-1。
Linear organic hole transport material manufactured in the present embodiment limits electric current (space charge by space
Limited current, SCLC) method test hole migration efficiency.Hole migration efficiency and current density and bias relation are as follows
Formula: μ=8d3J/9ε0εrV2, wherein d is hole film thickness (cm), and J is current density (mA/cm2),ε0For permittivity of vacuum
(8.85×10-14C V-1cm-1),εrFor constant 3, V is setting bias (V).Test results are shown in figure 3, according to test and formula
The hole migration efficiency of the linear organic hole transport material VII calculated is 1.55 × 10-4cm2.V-1.s-1。
Linear organic hole transport material manufactured in the present embodiment, sem test is as shown in figure 4, can be with from figure
Find out, hole transmission layer film forming is relatively smooth smooth, generates almost without graininess or empty shape, shows that linear organic hole passes
Defeated material VII has preferable dissolution film forming.
According to document Mabrouk, S.；Zhang,M.；Wang,Z.；Liang,M.；Bahrami,B.；Wu,Y.；Wu,J.；
Qiao Q.；Yang S.J.Mater.Chem.A, 2018,6,7950-7958 prepare perovskite solar battery and to its performances
It is tested, the structure of perovskite solar battery is as shown in Figure 5.Testing light source is (the solar simulator- of AM 1.5
Oriel 91160-1000,300W), data acquisition uses 2400 digital sourcemeter of Keithley.Linear organic sky of the present embodiment
The open-circuit voltage (Voc) of hole transport materials test result (I-V curve figure is shown in Fig. 6) display, battery is 1.094V, and short circuit current is close
Spending (Jsc) is 22.316mA cm-2, and fill factor (FF) is 0.756, photoelectric conversion efficiency 18.45%.
Embodiment 2
A kind of linear organic hole transport material, the difference from embodiment 1 is that, step 2 are as follows: in argon gas protection and ice
Under conditions of bath, 20mL anhydrous tetrahydro furan is added into reaction flask as solvent, 2.19g chemical compounds I is added and is uniformly mixed, then
The lithium diisopropylamine solution of 2mol/L is added dropwise in reaction system；It is added dropwise, reaction solution continues under ice bath
React 1h；Anhydrous cupric chloride is added in reaction system, the chemical compounds I, lithium diisopropylamine and anhydrous cupric chloride
The ratio of the amount of substance is 1:1.1:1.1, and after the 1h that is maintained under ice bath that the reaction was continued, reaction solution is to slowly warm up to the continuous reaction of room temperature
8h；Water quenching on the rocks is gone out, and ethyl acetate extraction, anhydrous magnesium sulfate is dry, and vacuum distillation removes solvent；Crude product chromatographs (leaching through column
Lotion: petroleum ether/methylene chloride=15/1) purification obtains compound ii, and obtained compound ii is light yellow solid, this step is anti-
The yield for answering compound ii is 62.5%.
Step 3 are as follows: under the protection of argon gas, sequentially added into three-necked flask 872mg compound ii, sodium tert-butoxide,
Tris(dibenzylideneacetone) dipalladium, 2,2'- be bis--(diphenyl phosphine) -1,1'- dinaphthalene, compound III and 25mL dry toluene, it is described
Compound ii, compound III, sodium tert-butoxide, tris(dibenzylideneacetone) dipalladium and 2,2'- it is bis--(diphenyl phosphine) -1,1'- dinaphthalene
Substance amount ratio be 1:1.3:4:0.05:0.15；Reaction system is heated to 110 DEG C of reaction 8h, is cooled to room temperature, and decompression is steamed
Solvent is removed in distillation, and crude product obtains compounds Ⅳ through column chromatography (eluent: petroleum ether/methylene chloride=15/1) purification, obtains
Compounds Ⅳ be faint yellow solid, this step compound of reaction IV yield be 78%.
Embodiment 3
A kind of linear organic hole transport material, the difference from embodiment 1 is that, step 3 are as follows: in argon gas protective condition
Under, 872mg compound ii, potassium tert-butoxide, tris(dibenzylideneacetone) dipalladium, 1,1'- bis- (two is sequentially added into three-necked flask
Phenylphosphine) ferrocene, compound III and 25mL dry toluene, the compound ii, compound III, potassium tert-butoxide, three (two benzal
Benzylacetone) ratios of amount of substance of two palladiums and bis- (diphenylphosphine) ferrocene of 1,1'- is 1:1.3:4:0.05:0.2；Reaction system
110 DEG C of reaction 8h are heated to, are cooled to room temperature, vacuum distillation removes solvent, and crude product chromatographs (eluent: petroleum ether/bis- through column
Chloromethanes=15/1) purification obtain compounds Ⅳ, obtained compounds Ⅳ be faint yellow solid, this step compound of reaction IV production
Rate is 32%.
Embodiment 4
A kind of linear organic hole transport material, the difference from embodiment 1 is that, step 3 are as follows: in argon gas protective condition
Under, 872mg compound ii, sodium tert-butoxide, [1,1'- bis- (diphenylphosphino) ferrocene] dichloro are sequentially added into three-necked flask
Change palladium, bis- (diphenylphosphine) ferrocene of 1,1'-, compound III and 25mL dry toluene, the compound ii, compound III, uncle
The amount of the substance of sodium butoxide, [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride and bis- (diphenylphosphine) ferrocene of 1,1'-
Ratio be 1:1.3:4:0.05:0.2；Reaction system is heated to 110 DEG C of reaction 8h, is cooled to room temperature, and vacuum distillation removes solvent,
Crude product obtains compounds Ⅳ through column chromatography (eluent: petroleum ether/methylene chloride=15/1) purification, and obtained compounds Ⅳ is
Faint yellow solid, the yield of this step compound of reaction IV are 1.5%.
Step 4 are as follows: under the conditions of argon gas protection and -78 DEG C, 234mg compounds Ⅳ and nothing are added into round bottom reaction flask
Water tetrahydrofuran, then n-BuLi (2.5mol/L) is added dropwise in reaction system.Be added dropwise, reaction solution continue-
2h is reacted at 78 DEG C, tributyltin chloride is added in reaction system, the compounds Ⅳ, n-BuLi and tributyl chlorination
The ratio of the amount of the substance of tin is 1:2.4:2.4；Reaction solution is to slowly warm up to room temperature the reaction was continued 8h；Water quenching on the rocks is gone out, acetic acid second
Ester extraction, anhydrous magnesium sulfate is dry, and vacuum distillation removes solvent；Crude product need not purify, and be directly used as the next step.
Step 5 are as follows: under argon gas protective condition, into three neck round bottom flask, successively by compound V, 461mg compound
VI, tetrakis triphenylphosphine palladium and 15mL toluene, the amount of the substance of the compound V, compound VI and tetrakis triphenylphosphine palladium
Ratio be 1:3:0.1；Reaction system is heated to 80 DEG C of reaction 8h and is cooled to room temperature, and vacuum distillation removes solvent；Crude product is through column
Chromatography (eluent: petroleum ether/methylene chloride=6/1) purification obtains compound VII, and compound VII is organic hole transport material,
Compound VII is yellow solid, and VII gross production rate of compound of two step of step 4 and step 5 is 36%.
Comparative example 1
A kind of organic hole transport material has chemical structural formula below:
Battery device circuit photocurrent density in hole is 22.6mA cm in comparative example 1-2, open-circuit voltage 1.01V, filling
The factor 0.71, incident photon-to-electron conversion efficiency reach 16.2% (referenced patent CN107915744A).
The present invention and the difference of the organic hole transport material of comparative example 1 are that molecule core becomes from dithieno pyrroles
For four bigger Thienopyrroles of conjugated degree, the hole mobility of the two remains basically stable, and can be preferable in chlorobenzene solvent
Ground dissolution film forming, but the linear organic hole transport material of the present invention is compared with 1 material of comparative example, conductivity and photo and thermal stability
It has a clear superiority, and battery efficiency improves 13.9%, it is shown that the linear organic hole transport material of the present invention has more excellent
Different photovoltaic performance has better practical application value.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of linear organic hole transport material, which is characterized in that the chemical structural formula with following formula (VII):
2. a kind of preparation method of linear organic hole transport material described in claim 1, which is characterized in that including following step
It is rapid:
Step 1, prepare compound I, compound III and compound VI, the structural formula of the chemical compounds I are as follows:
The structural formula of the compound III are as follows:
The structural formula of the compound VI are as follows:
Chemical compounds I is first reacted with lithium diisopropylamine, then reacts with anhydrous cupric chloride and generate compound ii, institute by step 2
State the structural formula of compound ii are as follows:
Compound ii and compound III are carried out Buchwald-Hartwig and are coupled cyclization reaction, generate compounds Ⅳ by step 3,
The structural formula of the compounds Ⅳ are as follows:
Compounds Ⅳ is first acted on n-BuLi, then reacts with tributyltin chloride and generate compound V, describedization by step 4
Close the structural formula of object V are as follows:
Compound V and compound VI are carried out Still coupling reaction, generate compound VII by step 5, and the compound VII is
Linear organic hole transport material.
3. a kind of preparation method of linear organic hole transport material according to claim 2, which is characterized in that the step
Rapid two are as follows: under argon gas protection and condition of ice bath, chemical compounds I is made to react 1~3h with lithium diisopropylamine, then to reaction system
Middle addition anhydrous cupric chloride, the reaction was continued under condition of ice bath 1~3h are warming up to room temperature the reaction was continued 8~16h, through isolating and purifying
Obtain compound ii；The ratio of the amount of the substance of the chemical compounds I, lithium diisopropylamine and anhydrous cupric chloride be 1:0.8~
1.2:0.8~1.2.
4. a kind of preparation method of linear organic hole transport material according to claim 2, which is characterized in that the step
Rapid three are as follows: under argon gas protective condition, in dry toluene solvent, make compound ii and compound III in palladium catalyst, organic phosphorus
Be heated to reflux under the catalytic action of ligand and organic base, occur Buchwald-Hartwig coupling reaction, the reaction time be 4~
12h, through isolating and purifying to obtain compounds Ⅳ；The compound ii, compound III, organic base, palladium catalyst and organophosphor ligand
Substance amount ratio be 1:1~1.5:2~8:0.02~0.1:0.04~0.2.
5. a kind of preparation method of linear organic hole transport material according to claim 2, which is characterized in that the step
Rapid four are as follows: under argon gas protective condition, in anhydrous tetrahydro furan solvent, make compounds Ⅳ under the conditions of -78 DEG C with n-BuLi
2h is reacted, tributyltin chloride is then added, is warming up to room temperature, the reaction was continued 4~12h obtains compound V；The compound
IV, the ratio of the amount of the substance of n-BuLi and tributyltin chloride is 1:2~2.5:2~2.5.
6. a kind of preparation method of linear organic hole transport material according to claim 2, which is characterized in that the step
Rapid five are as follows: under argon gas protective condition, in toluene solution, make compound V and compound VI under the catalysis of tetra-triphenylphosphine palladium
It is heated to reflux and Stille coupling reaction occurs, the reaction time is 4~12h, is isolated and purified to obtain compound VII, compound VII is
Linear organic hole transport material；The ratio of the amount of the substance of the compound V, compound VI and tetra-triphenylphosphine palladium be 1:2~
3:0.05~0.1.
7. a kind of preparation method of linear organic hole transport material according to claim 4, it is characterised in that: step 3
In, the palladium catalyst is palladium chloride, tris(dibenzylideneacetone) dipalladium, [1,1'- bis- (diphenylphosphino) ferrocene] dichloro
Change one of palladium or four triphenyl phosphorus palladiums or a variety of, the organophosphor ligand is tri-tert-butylphosphine, 1,1'- bis- (diphenylphosphines)
Ferrocene or 2,2'- is bis--one of (diphenyl phosphine) -1,1'- dinaphthalene or a variety of, the organic base is sodium tert-butoxide or tertiary fourth
One or both of potassium alcoholate.
8. a kind of application of the linear organic hole transport material described in claim 1 in perovskite solar battery.
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